Amino acids react with carbon dioxide (CO2) and form nanofibers and nanoflowers

ABSTRACT

A method for capturing CO 2  comprising dissolving at least one pure amino acid (AA) in water without the use of a catalyst for establishing protonation of an amino group of the amino acid, adding at least one base solution to the amino acid and water solution to deprotonate the protonated amino group of the amino acid and forming an amino acid-XOH—H 2 O wherein X is sodium or potassium, and subjecting CO 2  to the amino acid-XOH—H 2 O to form new nanomaterials is provided. A regenerable nanofiber is disclosed comprising a NaHCO 3  nanofiber, a KHCO 3  nanofiber, or an amino acid nanofiber made from subjecting a CO 2  gas to an amino acid aqueous solvent. Preferably, the amino acid aqueous solvent is one or more of a Gly-NaOH—H 2 O, an Ala-NaOH—H 2 O, a Phe-NaOH—H 2 O, a Gly-KOH—H 2 O, an Ala-KOH—H 2 O, and a Phe-KOH—H 2 O.

CROSS-REFERENCE TO RELATED APPLICATION

This utility non-provisional patent application claims the benefit of U.S. Provisional patent Application Ser. No. 62/345,282, filed on Jun. 3, 2016. The entire contents of U.S. Provisional Patent Application Ser. No. 62/345,282 is incorporated by reference into this utility patent application as if fully written herein.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under Grant No. RES DE-FE0004000 awarded by the Department of Energy, DOE/NETL. The government has certain rights in the invention.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention provides (i) nanomaterials such as bicarbonate nanoflowers and nanofibers, and (ii) a method for manufacturing these bicarbonate nanomaterials and amino acid nanofibers using an environmentally friendly approach, and (iii) a process of using these bicarbonate nanomaterials and amino acid nanofibers for capturing CO₂ which otherwise would be released into atmosphere such as for example by power generation facilities.

2. Background Art

One of the most promising fields in the manufacturing section is “nanomanufacturing” which has been a growing economy since many industrial sectors (such as aerospace, energy, transportation, and medicine) have been highly benefited and improved by the application of nanomaterials. Most of today's products involving nanomaterials are produced using top down conventional technologies, while the large facilities, needed for large-scale production, have a huge environmental impact. New methods of nanomaterials production that have less environmental impact or reduce environmental concerns are desirable to make nanomanufacturing more attractive to the industrial sector.

Meanwhile, human activity contributes ˜35 billion tons of carbon dioxide (CO₂), a major greenhouse gas, to the atmosphere every year. The accumulation of CO₂ in the atmosphere has been widely believed to be a major contributor to global climate change over decades [1, 2],

Unfortunately, despite the advances in alternative energy, future energy scenarios still include continuing growth in the absolute use of fossil energy[3, 4]. Concerns of the high level (ca. 400 ppm [5, 6]) of CO₂ in the atmosphere has therefore resulted in political targets and scientific/technological efforts to reduce CO₂ emission. In 2014, the U.S. Environmental Protection Agency proposed a regulation that would cut CO₂ emissions from existing coal plants by up to 30 percent by 2030 compared with the 2005 levels, which means cutting 550 million tons of CO₂ annually until 2030. The European Commission also proposed a 2030 climate and energy policy framework; a centerpiece of the framework is the target of reducing European Union domestic greenhouse gas emissions by 40% below the 1990 level by 2030 [7]. To achieve these goals, it is imperative that we explore innovative CO₂ capture and sequestration (CCS) technologies to reduce CO₂ emissions and to lower its concentration in the atmosphere [8, 9].

Most of today's products involving nanomaterials are produced using top down conventional technologies, while most nanomanufacturing process requires advanced and often very expensive equipment and facilities, and the large facilities have a huge environmental impact.

Meanwhile, current carbon capture and sequestration (CCS) technologies are very energy intensive, and CO₂ capture dominates in both energy consumption and cost[10, 11]. Aqueous amines and other methods of CO₂ capture have been extensively reviewed[12-14]. Among the various CO₂ capture technologies, solvent based technologies represent one of the leading options for large scale CO₂ capture[15]. Solvents primarily based on aqueous alkanolamine solutions such as monoethanolamine (MEA) are thought to be the most feasible process that may be readily adopted by existing power plants to capture a large amount of CO₂ [16]. After CO₂ absorption, the aqueous alkanolamine solutions are typically heated to 110° C. or higher to liberate the CO₂ for sequestration. This heating demands a high energy input and the subsequent sequestration demands many safe “carbon banks” which so far are limited[17] and may possess potential safety and leakage concerns[18].

A promising strategy to the current CCS technologies is to reduce CO₂ emissions via converting CO₂ into commercially valuable products[19]. For instance, CO₂ may be converted into urea, formic acid, salicylic acid, methanol, etc. [20, 21]; however, catalysts are required and current catalysts have low catalytic activity toward such conversions, and the product separation is difficult. CO₂ has also been converted into mineral byproducts such as carbonates and bicarbonates which can be sold or stored without the danger of CO₂ leakage and groundwater contamination[22]. In this case, sodium hydroxide (NaOH) has been long studied for removing CO₂ through generation of carbonate and bicarbonate in industry. More recently, Skyonic (San Antonio, Tex.) has developed an electrochemical production process to create NaOH to capture CO₂ and potentially to sell one of its products (i.e. NaHCO₃) as baking soda[22, 23]. However, the NaOH process in general suffers from inefficient mineralization[24].

The combination of CO₂ capture and conversion is an attractive strategy for reducing CO₂ emission to the atmosphere and meanwhile produces new nanomaterials that have great commercial values. In contrast to the background art, the present invention sets forth an unprecedented strategy, based on self-concentrating amino acids, such as for example but not limited to Glycine and Alanine salt solvents, to convert CO₂ into NaHCO₃ nanomaterials which are unique and have never been produced or reported. The disclosed invention will overcome problems such as the need for expensive catalysts, difficulty in product separation, and low CO₂ capture properties of the previous CO₂ conversion approaches. The NaHCO₃ and KHCO₃ nanomaterials of this invention can also be easily regenerated and reused if desired.

SUMMARY OF THE INVENTION

The present invention provides a method for capturing carbon dioxide comprising dissolving at least one amino acid in water, wherein the amino acid has an amino group located on one end of the amino acid's structure and a carboxyl group located on another end of the amino acid's structure, for protonating the amino group of the amino acid and forming a protonated amino acid, adding a base solution to the protonated amino acid for deprotonating the protonated amino group of the amino acid for forming an amino acid-XOH—H₂O solvent, and subjecting a gas containing carbon dioxide to the amino acid-XOH—H₂O solvent to form a carbamate, wherein X is preferably sodium or potassium. This method preferably includes wherein the base solution is for example, but not limited to, a sodium hydroxide solution or a potassium hydroxide solution.

Another embodiment of this invention includes the method for capturing carbon dioxide, as described herein, wherein the formed carbamate is subjected to hydrolysis to faun NaHCO₃ and the absorption of carbon dioxide without the use of a catalyst. This method includes wherein the NaHCO₃ is a sodium bicarbonate nanoflower or nanofiber.

Another embodiment of this invention includes the method for capturing carbon dioxide, as described herein, wherein the formed carbamate is subjected to hydrolysis to form potassium bicarbonate and the absorption of carbon dioxide without the use of a catalyst. This method includes wherein the potassium bicarbonate is a potassium bicarbonate nanoflower or nanofiber.

In another embodiment of this invention, a method for capturing carbon dioxide is provided comprising dissolving at least one amino acid in water, wherein the amino acid has an amino group located on one end of the amino acid's structure and a carboxyl group located on another end of the amino acid's structure, for protonating the amino group of the amino acid and forming a protonated amino acid, adding a base solution to the protonated amino acid for deprotonating the protonated amino group of the amino acid for forming an amino acid-XOH—H₂O solvent, and subjecting a gas containing carbon dioxide to the amino acid-XOH—H₂O solvent to form a carbamate, wherein X is preferably sodium or potassium, wherein the amino acid has a formula HOOC—RH—NH₂, wherein R is absent or wherein R is an alkyl group having from 1 to 5 carbon atoms, or a substituted alkyl group having from 1 to 5 carbon atoms, wherein the substitutions are one or more side chains or groups of the structures of known twenty amino acids. The known twenty amino acids are glycine, alanine, serine, threonine, cysteine, valine, leucine, isoleucine, methionine, proline, phenylalanine, tyrosine, tryptophan, aspartic acid, glutamic acid, asparagine, glutamine, histidine, lysine, and arginine. In a preferred embodiment of the method of this invention, the amino acid is selected from the group consisting of alanine (Ala), glycine (Gly) and phenylalanine (Phe). In a more preferred embodiment of the method of this invention, as described herein, the carbon dioxide containing gas is a flue gas, or a waste process stream having carbon dioxide.

Another embodiment of this invention provides a method of absorption of carbon dioxide gas from a process stream comprising subjecting the process stream containing carbon dioxide to a Glycine(Gly)-XOH—H₂O or an Alanine(Ala)-XOH—H₂O without the use of a catalyst to form a carbamate, wherein X is sodium or potassium, for absorption of CO₂. In a preferred embodiment of this method, as described herein, X is sodium and includes subjecting the carbamate to undergo hydrolysis to form a sodium bicarbonate (NaHCO₃). In a more preferred embodiment of this method, as described herein, the NaHCO₃ is in the form of a nanoflower or nanofiber. In another preferred embodiment of this method, as described herein, X is potassium and includes subjecting the carbamate to undergo hydrolysis to form a potassium bicarbonate (KHCO₃). In another more preferred embodiment of this method, as described herein, the KHCO₃ is in the form of a nanoflower or nanofiber.

Another embodiment of this invention provides a regenerable nanofiber comprising a NaHCO₃ nanofiber, a KHCO₃ nanofiber, or an amino acid nanofiber made from subjecting a CO₂ containing gas to an amino acid aqueous solvent without the use of a catalyst. The regenerable nanofiber of this invention, as described herein, includes wherein the amino acid aqueous solvent is selected from the group consisting of Gly-NaOH—H₂O, Ala-NaOH—H₂O, Phe-NaOH—H₂O, Gly-KOH—H₂O, Ala-KOH—H₂O, and Phe-KOH—H₂O.

Another embodiment of this invention provides a method for producing nanomaterials comprising subjecting a flue gas having carbon dioxide or a carbon dioxide greenhouse gas to an amino acid containing aqueous solution without the use of a catalyst for producing a nanomaterial. This method includes wherein the amino acid containing aqueous solution is selected from the group consisting of Gly-NaOH—H₂O, Ala-NaOH—H₂O, Phe-NaOH—H₂O, Gly-KOH—H₂O, Ala-KOH—H₂O, and Phe-KOH—H₂O. In a preferred embodiment of this method, as described herein, includes wherein the amino acid containing solution is Gly-NaOH—H2O and the resulting nanomaterial is sodium bicarbonate nanomaterial. In a more preferred embodiment of this method, as described herein, the resulting sodium bicarbonate nanomaterial is regenerable and reusable. In another preferred embodiment of this method, as described herein, includes wherein the amino acid containing solution is Gly-K—OH—H2O and the resulting nanomaterial is potassium bicarbonate nanomaterial. In a more preferred embodiment of this method, as described herein, the resulting potassium bicarbonate nanomaterial is regenerable and reusable.

In yet another embodiment of this invention, a solvent is provided comprising at least one amino acid, water, and a base solution, wherein the amino acid(s) is/(are) dissolved in the water and the base solution. In a preferred embodiment of this invention, the solvent, as described herein, wherein the base solution is one selected from a NaOH solution or a KOH solution to form an amino acid-XOH—H₂O solvent wherein X is Na or K. The solvent includes wherein the amino acid is one or more of the amino acids selected from the group of glycine, alanine, serine, threonine, cycteine, valine, leucine, isoleucine, methionine, proline, phenylalanine, tyrosine, tryptophan, aspartic acid, glutamic acid, asparagine, glutamine, histidine, lysine, and arginine. More preferably, the solvent of this invention, as described herein, includes wherein the amino acid is one or more of glycine, alanine, or phenylalanine. In another embodiment of this invention, the solvent, as described herein, is a mixture of two or more of the amino acids. In another embodiment of this invention, the solvent, as described herein, is a mixture of two or more of the amino acids and two or more of the base solutions. In a most preferred embodiment, the solvent of this invention, as described herein, is self-concentrating.

These and other aspects of this invention will be more fully understood from the following detailed description of the invention, the figures, and the claims appended hereto.

BRIEF DESCRIPTION OF THE DRAWINGS

This invention is further illustrated by the following non-limited figures:

FIG. 1A is a schematic that shows Gly-NaOH—H₂O turns CO₂ into regenerable NaHCO₃ nano fibers. The schematic shows a cycle of the CO₂ absorption and desorption processes of regenerable NaHCO₃ nanofibers.

FIG. 1B is a field emission scanning electron microscope (FE-SEM) image of nanofibers obtained in Gly-NaOH—H₂O solution. The CO₂ absorption time was 25 minutes.

FIG. 1C is a FE-SEM image of Gly-NaOH—H₂O solution after CO₂ absorption, desorption, and re-absorption.

FIG. 1D is a histogram showing the diameter distribution of NaHCO₃ nanofibers presented in (FIG. 1B).

FIG. 1E is a ′H NMR (upper) and ′³C NMR (lower) spectra of Gly-NaOH—H₂O solution after CO₂ absorption.

FIG. 1F is an EDX spectrum of single NaHCO₃ nanofibers.

FIG. 1G shows a cyclic CO₂ absorption and desorption performance of Gly-NaOH—H₂O solution.

FIG. 2A is a SEM image that shows the effect of CO₂ absorption time on formation of NaHCO₃ nanofibers, specifically, a SEM image at CO₂ absorption of 2 minutes.

FIG. 2B is an SEM image at CO₂ absorption of 5 minutes.

FIG. 2C is an SEM image at CO₂ absorption of 10 minutes.

FIG. 2D is an SEM image at CO₂ absorption of 15 minutes.

FIG. 2E is an SEM image at CO₂ absorption of 25 minutes.

FIG. 2F is an SEM image at CO₂ absorption of ′H NMR.

FIG. 2G is an SEM image at CO₂ absorption of ¹³C NMR spectra for Gly-NaOH—H₂O solution at varying absorption time. Tetramethylammonium chloride [(CH])4N⁺Cl], used as a standard reference for quantitative determination of species, shows peaks at 3.05 and 55.10 ppm in ′H NMR and ¹³C NMR spectra, respectively.

FIG. 2H shows species changes in Gly-NaOH—H₂O solution as a function of CO₂ absorption time from NMR spectra.

FIG. 3A is an image of Ala-NaOH—H₂O solution after CO₂ absorption.

FIG. 3B is an typical FE-SEM image of solid precipitates formed in self-concentrating Ala-NaOH—H₂O solution. Inset shows a high-resolution FE-SEM image of a flower of NaHCO₃ nanowires.

FIG. 3C is an EDX spectra of Ala particles (Lipper) and NaHCO₃ nanowires (lower).

FIG. 3D is a ′H NMR (upper) and ¹³C NMR (lower) spectra of lean phase. Tetramethylammonium chloride [(CH3)4N⁺Cr] was used as a standard reference.

FIG. 3E is a ′H NMR (upper) and ¹³C NMR (lower) spectra of solid mixes.

FIG. 4 shows CO₂ uptake performance of Ala-NaOH—H₂O solvent of this invention.

FIG. 5 shows species changes (from NMR spectra) in Ala-NaOH—H₂O as a function of CO₂ absorption time.

FIG. 6A is a schematic that shows the purification process of solid mixes to obtain NaHCO₃ solids of this invention. Ala-NaOH—H₂O solution absorbs CO₂ and undergoes a self-concentrating process to form a CO₂-lean phase and a CO₂-rich phase with solid precipitates. The CO₂-rich phase undergoes a simple rinsing process, during which Ala and Ala carbamate solids dissolve in the rinsing water and are removed and reused; NaHCO₃ solids are left and may be used as a valuable product (e.g. baking soda).

FIG. 6B shows the purification of solid mixes to obtain NaHCO₃ solids, ′H NMR (upper) and C (lower) NMR spectra of remained solids after rinsing,

FIG. 6C shows the purification of solid mixes to obtain NaHCO₃ solids with species percentage in remaining solids before and after rinsing. The concentration of Ala in the Ala-NaOH—H₂O solution was 17 wt % (weight percent) with a molar ratio of Ala:NaOH=1:2. In continuous stirred-tank reactor (CSTR) studies, Ala salt solution also converted CO₂ into NaHCO₃ nanoflowers and had high CO₂ absorption performance.

FIG. 7A shows the results of CSTR studies: CO₂ absorption performance of Ala-NaOH—H₂O (i.e. the solvent of the present invention), MEA-H₂O, and NaOH—H₂O control solutions. Inset shows the CSTR reactor schematic. To examine the potential for large scale studies, Ala-NaOH—H₂O solution was also examined and compared with MEA-H₂O and NaOH—H₂O solutions under a simulated flue gas (10% CO₂ and 90% N₂) in CSTR. Monoethanolamine (MEA) is thought to be one of the most feasible processes for capturing a large amount of CO₂ that may be easily adopted by existing plants. [16]

FIG. 7B shows the species changes as a function of CO₂ absorption time.

FIG. 8 is a FE-SEM image of solid precipitates formed in NaOH control solution.

FIG. 9 shows the results of a CSTR study of CO₂ absorption performance of Ala-H₂O solution (i.e. without NaOH).

FIG. 10 shows the morphology of amino acid nanofibers (i.e, phenylalanine nanofibers) formed during CO₂ bubbling into Phe-NaOH—H₂O solution.

FIG. 11 shows CO₂ uptake in Phe-NaOH—H₂O solution. Phe-0.2M-NaOH—CO₂-precipitate (H₂O washed).

FIG. 12 shows NMR data of the nanofibers formed during CO₂ bubbling into Phe-NaOH—H₂O solution of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a method for capturing carbon dioxide comprising dissolving at least one amino acid in water, wherein the amino acid has an amino group located on one end of the amino acid's structure and a carboxyl group located on another end of the amino acid's structure, for protonating the amino group of the amino acid and forming a protonated amino acid, adding at least one base solution to the protonated amino acid for deprotonating the protonated amino group of the amino acid for forming an amino acid-XOH—H₂O solvent, and subjecting a gas containing carbon dioxide to the amino acid-XOH—H₂O solvent to form a carbamate, wherein X is preferably sodium or potassium. This method preferably includes wherein the base solution is for example, but not limited to, a sodium hydroxide solution or a potassium hydroxide solution.

Another embodiment of this invention includes the method for capturing carbon dioxide, as described herein, wherein the formed carbamate is subjected to hydrolysis to form NaHCO₃ and the absorption of carbon dioxide without the use of a catalyst. This method includes wherein the NaHCO₃ is a sodium bicarbonate nanoflower or nanofiber.

Another embodiment of this invention includes the method for capturing carbon dioxide, as described herein, wherein the formed carbamate is subjected to hydrolysis to form potassium bicarbonate and the absorption of carbon dioxide without the use of a catalyst. This method includes wherein the potassium bicarbonate is a potassium bicarbonate nanoflower or nanofiber.

In another embodiment of this invention, a method for capturing carbon dioxide is provided comprising dissolving at least one amino acid in water, wherein the amino acid has an amino group located on one end of the amino acid's structure and a carboxyl group located on another end of the amino acid's structure, for protonating the amino group of the amino acid and forming a protonated amino acid, adding at least one base solution to the protonated amino acid for deprotonating the protonated amino group of the amino acid for foaming an amino acid-XOH—H₂O solvent, and subjecting a gas containing carbon dioxide to the amino acid-XOH—H₂O solvent to form a carbamate, wherein X is preferably sodium or potassium, wherein the amino acid has a formula HOOC—RH—NH₂, wherein R is absent or wherein R is an alkyl group having from 1 to 5 carbon atoms, or a substituted alkyl group having from 1 to 5 carbon atoms, wherein the substitutions are one or more side chains or groups of the structures of known twenty amino acids. The known twenty amino acids are glycine, alanine, serine, threonine, cysteine, valine, leucine, isoleucine, methionine, proline, phenylalanine, tyrosine, tryptophan, aspartic acid, glutamic acid, asparagine, glutamine, histidine, lysine, and arginine, in a preferred embodiment of the method of this invention, the amino acid is selected from the group consisting of alanine (Ala), glycine (Gly) and phenylalanine (Phe). In a more preferred embodiment of the method of this invention, as described herein, the carbon dioxide containing gas is a flue gas, or a waste process stream having carbon dioxide.

Another embodiment of this invention provides a method of absorption of carbon dioxide gas from a process stream comprising subjecting the process stream containing carbon dioxide to a Glycine(Gly)-XOH—H₂O or an Alanine(Ala)-XOH—H₂O without the use of a catalyst to form a carbamate, wherein X is sodium or potassium, for absorption of CO₂. In a preferred embodiment of this method, as described herein, X is sodium and includes subjecting the carbamate to undergo hydrolysis to form a sodium bicarbonate (NaHCO₃). In a more preferred embodiment of this method, as described herein, the NaHCO₃ is in the form of a nanoflower or nanofiber. In another preferred embodiment of this method, as described herein, X is potassium and includes subjecting the carbamate to undergo hydrolysis to form a potassium bicarbonate (KHCO₃). In another more preferred embodiment of this method, as described herein, the KHCO₃ is in the form of a nanoflower or nanofiber.

Another embodiment of this invention provides a regenerable nanofiber comprising a NaHCO₃ nanofiber, a KHCO₃ nanofiber, or an amino acid nanofiber made from subjecting a CO₂ containing gas to an amino acid aqueous solvent without the use of a catalyst. The regenerable nanofiber of this invention, as described herein, includes wherein the amino acid aqueous solvent is selected from the group consisting of Gly-NaOH—H₂O, Ala-NaOH—H₂O, Phe-NaOH—H₂O, Gly-KOH—H₂O, Ala-KOH—H₂O, and Phe-KOH—H₂O.

Another embodiment of this invention provides a method for producing nanomaterials comprising subjecting a flue gas having carbon dioxide or a carbon dioxide greenhouse gas to an amino acid containing aqueous solution without the use of a catalyst for producing a nanomaterial. This method includes wherein the amino acid containing aqueous solution is selected from the group consisting of Gly-NaOH—H₂O, Ala-NaOH—H₂O, Phe-NaOH—H₂O, Gly-KOH—H₂O, Ala-KOH—H₂O, and Phe-KOH—H₂O. In a preferred embodiment of this method, as described herein, includes wherein the amino acid containing solution is Gly-NaOH—H2O and the resulting nanomaterial is sodium bicarbonate nanomaterial. In a more preferred embodiment of this method, as described herein, the resulting sodium bicarbonate nanomaterial is regenerable and reusable. In another preferred embodiment of this method, as described herein, includes wherein the amino acid containing solution is Gly-K—OH—H2O and the resulting nanomaterial is potassium bicarbonate nonmaterial. In a more preferred embodiment of this method, as described herein, the resulting potassium bicarbonate nanomaterial is regenerable and reusable.

In yet another embodiment of this invention, a solvent is provided comprising at least one amino acid, water, and a base solution, wherein the amino acid(s) is (are) dissolved in the water and the base solution. In a preferred embodiment of this invention, the solvent, as described herein, wherein the base solution is one selected from a NaOH solution or a KOH solution to form an amino acid-XOH—H₂O solvent wherein X is Na or K. The solvent includes wherein the amino acid is one or more of the amino acids selected from the group of glycine, alanine, serine, threonine, cycteine, valine, leucine, isoleucine, methionine, proline, phenylalanine, tyrosine, tryptophan, aspartic acid, glutamic acid, asparagine, glutamine, histidine, lysine, and arginine. More preferably, the solvent of this invention, as described herein, includes wherein the amino acid is one or more of glycine, alanine, or phenylalanine. In another embodiment of this invention, the solvent, as described herein, is a mixture of two or more of the amino acids. In another embodiment of this invention, the solvent, as described herein, is a mixture of two or more of the amino acids and two or more of the base solutions. In a most preferred embodiment, the solvent of this invention, as described herein, is self-concentrating.

Those persons skilled in the art will understand that the present invention provides (i) new nanomaterials such as for example but not limited to bicarbonate nanoflowers and nanofibers, which have never been produced, and (ii) a method for manufacturing these nanomaterials using an environmentally friendly approach including where we can manufacture bicarbonate nanomaterials and amino acid nanofibers and simultaneously capture CO₂, which otherwise would be released into atmosphere, from power generation facilities (i.e. power plants). In one case (i.e. the production of bicarbonate nanomaterials), the CO₂ is actually converted into a commercially useful product. Our new nanomanufacturing approach is performed entirely in an aqueous (no organic solvent) environment while utilizing little to literally no energy.

We have invented the approach to produce sodium bicarbonate nanoflowers and nanofibers, and this approach can be used to produce other nanomaterials such potassium bicarbonate, calcium bicarbonate, etc. We also produced amino acid nanofibers which could be 3D aligned nanofibers.

In other words, to reduce CO₂ emission from power plants etc., we developed innovative CO₂ capture and utilization technologies to (i) turn CO₂ into NaHCO₃ nanofibers and nanoflowers, (ii) self concentrate NaHCO₃ nanomaterials for easy separation and reuse, and (iii) develop an approach that will lead to both CO₂ absorption and amino acid nanofiber formation. Our technology will capture CO₂ and convert it into commercial products.

For the first time, CO₂ will be converted into nanomaterials and the conversion does not need any catalysts. The present process is simple, environmentally friendly, and is very unique. The present invention contributes significantly to the safe and economical capture of CO₂ from flue gas and meets the government's goal to reduce U.S. greenhouse gas emissions by up to 30 percent by 2030 compared with the 2005 levels. The methods of the present invention also produce new important nanomaterials that have great commercial value besides reducing CO₂ emission.

Advantages of the Present Invention

First, we have invented a new approach to produce nanomaterials such as bicarbonates which have never been produced by any other approaches. Our new nanomanufacturing approach is performed entirely in an aqueous (no organic solvent) environment while utilizing little to literally no energy. Such a technology is cost effective and environmentally friendly.

Our new nanomanufacturing technology meanwhile allows us to achieve CO₂ capture and utilization at the same time; specifically, we provide a self-concentrating amino acid (SCAA) solvent that turns CO₂ emission into NaHCO₃ nanofibers or nanoflowers, which have great commercial potential. This unique self-concentrating solvent enables us to obtain high CO₂ capture capacity and commercially valuable chemicals, offering a great benefit for a real CO₂ capture process. By adapting this process to the absorption of CO₂ from waste streams, or process streams, significant advantages over current technologies ensue, for example, but not limited to:

(A) Use NaHCO₃ nanofibers and nanowires as the final products (i.e. CO₂ conversion and utilization):

-   -   i. For the first time, this technology converts CO₂ emission         into unique NaHCO₃ nanofibers and nanoflowers with high CO₂         capacity.     -   ii. Unlike processes that physically remove the CO₂ to a remote         site^([25]) the industrial-scale generation of sodium         bicarbonate directly converts the undesirable CO₂ gas into         nanomaterials or chemicals at the point of power-generation.         Because the by-products of the CO₂ capture process are         economically useful, the value of these products offsets the         costs of capture; in properly designed systems, the capture         process can become profitable in itself. Unlike aqueous         amine-based solvents, which require heating to regenerate the         solvent, our technique involves the production of beneficial         products, which does not require any regeneration energy.     -   iii. In the literature, CO₂ may be converted into urea, formic         acid, salicylic acid, methanol, etc. [20, 21], however,         catalysts are required while current catalysts have low         catalytic activity toward such conversions, and the product         separation is difficult. In this disclosure, CO₂ is converted         into NaHCO₃ nanomaterials without the use of catalysts.         Moreover, the self-concentrating property enables easy         separation of the converted products.

(B) Regenerate the produced NaHCO₃ nanofibers and nanowires and reuse the materials for multiple cyclic CO₂ capture (i.e. capture CO₂ for CCS):

-   -   i. Unlike other decarbonation efforts that are not amenable to         retrofitting, embodiments of the present system may be         retrofitted to existing power-plants, greatly lowering the         capital costs necessary to remove CO₂. In addition, the CO₂         capture processing is scalable (from pilot scale to intermediate         scale to full scale implementation) by the addition of         incremental reactor units.     -   ii. Compared to monoethanolamine (MEA) solvents, the proposed         amino acid (AA) salt solutions typically have significantly         lower vapor pressures thereby resulting in reduced solvent loss.         Furthermore, AA salts typically have greater resistance to         oxidative degradation and lower toxicity than typical         alkanolamine solvents.^([26,28])     -   iii. Compared to NaOH scrubbing, the SCAA solvent process has         converted CO₂ into unique NaHCO₃ nanoflowers and has shown a         higher CO₂ capacity and faster absorption, which may reduce the         size of reactors and materials handling equipment, thereby         lowering capital costs.^([29])     -   iv. The produced NaHCO₃ could be regenerated at much lower         temperatures where biocatalysts can be better applied compared         to current technologies.

(C) Fabrication of amino acid nanofibers through a process that captures CO₂:

-   -   i. Besides CO₂ absorption, high quality and large quantities of         amino acid nanofibers can be produced and may serve as         commercial products. The process is simple. Again, amino acids         have their advantages (e.g. stability) as compared to other         materials.         The use of this invention is not restricted to carbon capture.         For example but not limited to, it may also be applied to:     -   (i) A simple new method to produce nanomaterials. Nanomaterials         such as NaHCO₃ nanofibers and nanoflowers can be synthesized by         simply bubbling acidic greenhouse gases such as CO₂ or a         simulated flue gas into Glycine and Alanine solutions.     -   (ii) A new process to produce high-purity soda nanomaterials. By         taking advantage of the unique self-concentrating phenomenon,         high-purity soda could be obtained via a simple rinsing         procedure (see FIG. 6).     -   (iii) A process to simultaneously capture CO₂ and obtain amino         acid nanofibers. By taking advantage of the self-assembly         properties of certain amino acids, easy formation and separation         of amino acid nanofibers and NaHCO₃ solids can be achieved.     -   (iv) A new method to produce inorganic and organic         nanomaterials.     -   (v) Converting CO₂ without the use of catalysts. In the         literature, CO₂ may be converted into urea, formic acid,         salicylic acid, or methanol; however, catalysts are required         while current catalysts have low catalytic activity toward such         conversions, and the product separation is difficult. In this         disclosure, CO₂ is converted into NaHCO₃ nanomaterials without         the use of catalysts. Moreover, the self-concentrating property         enables easy separation of the converted products.

Data and Results

The self-concentrating amino acid (SCAA) solvent of this invention was used to turn CO₂ into NaHCO₃ nanomaterials or baking soda. The work was based on the use of biological materials (amino acids, peptides, proteins, etc.) that we have studied in the context of drug delivery research (controlled and targeted drug capture and release).[30-34]

Materials used in the examples are: CO₂ gas, amino acids (for example, but not limited to, Gly, Ala, and Phe), and NaOH.

Solvent Preparation and the Mechanism of CO₂ Capture.

In the SCAA (self-concentrating amino acid) process, one or more amino acids (AAs) are used for the absorption of CO₂. When a pure amino acid (AA), with the overall formula HOOC—R—NH₂, is dissolved in water, the following equilibria are established:[35-38]

It is thus seen that, in solution, the neutral molecule takes the form of a dipole, because the carboxylic group loses a proton while the amine group is protonated. To absorb CO₂, the AAs are first neutralized with a base, for example but not limited to, a NaOH solution or a KOH solution. The base of NaOH is used below, for example: ⁻OOC—R—NH₃ ⁺+NaOH

Na⁺+⁻OOC—R—NH₂+H₂O The neutralized AA can then react with CO₂ in much the same way as “normal” amines, i.e. forming carbamate and/or bicarbonate: Carbamate Formation: CO₂+2Na⁺[⁻OOC—R—NH₂]

[Na⁺]₂[⁻OOC—R—NH—COO⁻]+⁻OOC—R—NH₃ ⁺  (1) Carbamate Hydrolysis and Bicarbonate Formation: [Na⁺]₂[⁻OOC—R—NH—COO³¹]+H₂O

Na⁺[⁻OOC—R—NH₂]+NaHCO₃  (2) Therefore, the addition of a base, as described above, is required and its role is to deprotonate the protonated amino group. After deprotonation, AAs react with CO₂ to form carbamate, which further undergoes hydrolysis to form NaHCO₃. As a result, CO₂ is absorbed.

Experimental Feasibility

We examined the absorption of CO₂ by Glycine(Gly)-NaOH—H₂O and Alanine(Ala)-NaOH—H₂O first in 100% CO₂ followed by experiments in a simulated flue gas.

(1) Gly-NaOH—H₂O turns CO₂ into regenerable NaHCO₃ nanofibers:

CO2 was bubbled (FIG. 1A) into Gly-NaOH—H₂O solution for 25 minutes (min). For the first time, long nanofibers were formed in the Gly-NaOH—H₂O solution (FIG. 1B). The nanofibers were tens of micrometers long and their average diameter was about 45 nanometer (nm); the majority (over 80%) of the nanofibers were in the range of 30-55 nm (FIG. 1D). Nuclear magnetic resonance (NMR) studies found that NaHCO₃, Gly/GlyH⁺, and Gly carbamate were presented in the Gly-NaOH—H₂O solution upon CO₂ absorption (FIG. 1E). Further characterization of the nanofibers by energy dispersive X-ray (EDX) spectroscopy found sodium, oxygen, and carbon but no nitrogen in the nanofibers (FIG. 1F). These NMR and EDX studies suggested that the nanofibers were NaHCO₃. These findings mean that CO₂ can be converted into inorganic nanofibers, for example but not limited to NaHCO₃ nanofibers (i.e. bubbling CO₂ in Gly-NaOH—H₂O solutions), allowing easy production of inorganic nanofibers while reducing CO₂ emission. NaHCO₃ solids usually exist in the form of crystals and, to our knowledge, no NaHCO₃ nanoparticles or nanofibers have even been reported in the literature.

Interestingly, we found that the NaHCO₃ nanofibers could be easily regenerated in the Gly-NaOH—H₂O solution. After heating the solution (after CO₂ absorption) at 383K for 10 min (minutes), no nanofibers were observed. However, NaHCO₃ nanofibers were formed again (FIG. 1C) after bubbling CO₂ in the regenerated Gly-NaOH—H₂O solution. It seems that the Gly-NaOH—H₂O solution had a two-stage CO₂ absorption: In the first stage, the CO₂ absorption capacity increased very quickly and reached a capacity of [(0.37 mol CO₂)/(mol Gly)] within the first 2 min, and in the second absorption stage, the CO₂ absorption continued to increase but at a much slower rate compared to that of the first stage (FIG. 1G). A significant capacity of [−(0.64 mol CO₂)/(mol Gly)] was obtained and the solution could be regenerated and reused (FIG. 1G). Therefore, Gly-NaOH—H₂O solution could be used to absorb CO₂ while producing NaHCO₃ nanofibers and could be easily regenerated with a thermal swing process. Note that no NaHCO₃ specie was observed in the Gly-NaOH—H₂O solution after CO₂ absorption; this may indicate that, in the Gly-NaOH—H₂O solution, it is difficult for NaOH to react with CO₂ to form Na₂CO₃, which is the main product if NaOH dissolved in H₂O alone is used to absorb CO₂.

We further performed FE-SEM and NMR studies to examine NaHCO₃ nanofiber formation and species changes in the Gly-NaOH—H₂O solution as a function of CO₂ absorption time (FIGS. 2A-H). No NaHCO₃ nanofibers were observed before 2 min (FIG. 2A), nanofibers were formed at 5 min (FIG. 2B), and more NaHCO₃ nanofibers were produced with further increasing CO₂ absorption time (FIG. 2B-E). Correspondingly, NMR data showed that no NaHCO₃ species were detected before 2 min, while NaHCO₃ was formed at 5 min and kept increasing with increasing CO₂ absorption time (FIGS. 2F-H). Meanwhile, the amount of Gly carbamate increased sharply from 0 to 2 min, then increased at a much slower rate (compared to the first 2 min) with increasing CO₂ absorption time during 2-10 min, after which the amount of Gly carbamate decreased with further increasing CO₂ absorption time (FIG. 2F-H).

(2) In 100% CO₂, Alanine (Ala) salt solution converted CO₂ into NaHCO₃ nanoflowers and had high CO₂ absorption performance:

We found that Ala-NaOH—H₂O solution formed, after bubbling with 100% CO₂, two “phases” with the top clear phase (−½ in volume) and the bottom “milky” phase (−½ in volume. FIG. 3A). FE-SEM and elemental (EDX) analyses found that the “milky” phase had NaHCO₃ nanoflowers and Ala particles (FIGS. 3B and 3C). The nanoflowers were comprised of bunches of NaHCO₃ nanowires, which were about (˜) 50 nm in diameter and about 15 μm in length (FIG. 3B). Nuclear magnetic resonance (NMR) studies showed that NaHCO₃, Ala/AlaH⁺, and Ala carbamate were found in both the clear phase and the “milky” phase (FIGS. 3D and 3E). In the solid mixes, NaHCO₃ was dominant and the amounts of NaHCO₃, Ala/AlaH⁺, and Ala carbamate were 73.5, 23.5, and 3.0 wt %, respectively (FIG. 3E). In the clear phase, AIa/AlaH⁺ was dominant and the amounts of NaHCO₃, Ala/AlaH⁺, and Ala carbamate were about 15.0, about 65.0, and about 20.0 wt %, respectively (FIG. 3D).

A two-stage CO₂ absorption was observed in Ala-NaOH—H₂O solution: The CO₂ absorption capacity increased sharply first followed with a much slower CO₂ absorption before it plateaued (FIG. 4). The CO₂ absorption capacity of Ala-NaOH—H₂O solution (including the two phases) was found to be (1.78 mol CO₂)/(mol Ala) (FIG. 4). Note that the formation of the solids, which shifts the equilibrium of the reactions (1) and (2) toward the formation of carbamate or bicarbonate, likely have contributed to the high CO₂ absorption capacity. This is consistent with the observations by Kumar et al. who achieved higher CO₂ absorption capacity when amino acid precipitated.′³⁹¹ Interestingly, over 90% of the CO₂ absorbed by the Ala-NaOH—H₂O solution was in the “milky” phase and the majority (˜95%) of the CO₂ was absorbed in the form of NaHCO₃ nanoflowers. In other words, Ala-NaOH—H₂O solution self-concentrated into a CO₂-lean phase (i.e. the clear phase) and a CO₂-rich phase (i.e. the “milky” phase) upon bubbling with CO₂.

NMR spectra at different CO₂ absorption times revealed that Ala carbamate formed immediately after bubbling CO₂ into Ala-NaOH—H₂O solution, and the amount of Ala carbamate increased sharply from 0 to 2 min and then decreased with increasing CO2 absorption time (FIG. 5). No NaHCO₃ was detected before 2 min. NaHCO₃ started to form at 5 min and its amount increased rapidly from 5 to 30 min followed by an increase at a much slower rate from 30 to 90 min with increasing CO₂ absorption time (FIG. 5). At 30 min, there were ˜1.75 mol/(mol Ala) of NaHCO₃ and ˜0.13 mol/(mol Ala) of Ala carbamate (FIG. 5). Obviously, CO₂ reacted first with Ala in the Ala-NaOH—H₂O solution to form Ala carbamate which later hydrolyzed into NaHCO₃, in agreement with the aforementioned reactions (1) and (2).

Solid precipitates have been reported in some AAs when they interact with CO₂. Different precipitates have been reported depending on the AA structures and solubilities. ^([37,40]) For instance, Hook first reported the formation of carbonate precipitates in aqueous potassium salts of N-methylalanine and α-aminoisobutyric acid (and their sterically hindered derivatives) upon reacting with CO₂.^([41]) Versteeg and co-workers found that, upon interacting with CO₂, AAs (e.g. taurine) formed precipitates of AA zwitterions and possibly a small portion of bicarbonate. ^([42]) Precipitation of AAs are due to the decrease of pH during CO₂ bubbling since the solubility of AAs decreases with decreasing pH. To our knowledge, however, none of the previous studies had formed NaHCO₃ nanoflowers and there was no clear separation of the CO₂-lean and CO₂-rich phases. Therefore the unique characteristics of the Ala-NaOH—H₂O solution presented here include (i) the formation of NaHCO₃ nanoflowers and the majority of the CO₂ absorbed was in the form of NaHCO₃; nanoflowers, (ii) the clear separation of the CO₂-lean and CO₂-rich phases, (iii) the CO₂-rich phase having over 90% of the CO₂ absorbed by the whole solution, and (iv) the CO₂-rich phase possessing a small volume (i.e. ˜½ of the total volume).

These unique properties of the self-concentrating amino acid solvents of the present invention, for example but not limited to the Ala-NaOH—H₂O solution, offer the opportunity to obtain bicarbonate solids potentially as a commercially valuable chemical (e.g. baking soda). Since bicarbonate (73.5 wt %) was dominant in the solid mixes in the Ala-NaOH—H₂O solution, a simple process was designed (FIG. 6A); CO₂ is absorbed in Ala-NaOH—H₂O solution which self-concentrates and forms two distinct phases of CO₂-lean and CO₂-rich phases. The latter is separated from the CO₂-lean phase and undergoes a simple water rinsing step, during which solid Ala and its carbamate, and a small portion of bicarbonate dissolve and can be reused; Ala has a much higher solubility than NaHCO₃ in water at room temperature[43-45]. As a result, bicarbonate solid with a high purity can be achieved. Indeed, NaHCO₃, Ala/AlaH⁺, and Ala carbamate were present in the solid mixes before rinsing while, after rinsing with deionized water, only bicarbonate solids were obtained (FIGS. 6B and 6C) and more than 90% (ninety percent) of the bicarbonate solids was recovered. Note that bicarbonate solids could potentially be fully recovered if the solid mixes were rinsed with bicarbonate-saturated water. The significance of obtaining bicarbonate solids to serve as a potential commercial product include (i) offsetting the CO₂ capture costs by offering a commercially valuable product, (ii) eliminating the energy required for regeneration, (iii) reducing the concerns associated with the potential leakage of sequestered CO₂[46], and (iv) avoiding the transportation costs of conventional mineralization products to a sequestration site^([22]).

(3) In continuous stirred-tank reactor (CSTR) studies, Ala salt solution also converted CO₂ into NaHCO₃ nanoflowers and had high CO₂ absorption performance:

To examine the potential for large scale studies, Ala-NaOH—H₂O) solution was also examined and compared with MEA-H₂O and NaOH—H₂O solutions under a simulated flue gas (10% CO₂ and 90% N₂) in CSTR (FIGS. 7A and 7B). Monoethanolamine (MFA) is thought to be one of the most feasible processes for capturing a large amount of CO₂ that may be easily adopted by existing plants. ^([16])

Similar to the findings in 100% CO₂ and at small sample sizes, Ala-NaOH—H₂O solution in the CSTR studies had distinct separation of two phases (i.e. a top clear phase and a bottom “milky” phase of NaHCO₃ nanoflowers and Ala particles). The Ala-NaOH—H₂O solution also showed a clear two-stage CO₂ absorption: In the first absorption stage (I), the CO₂ absorption capacity increased linearly with increasing absorption time until about (˜) 360 min. In the second absorption stage (II), the CO₂ absorption continued to increase almost linearly, although at a much slower rate compared to that of the first stage, until a capacity of ˜(1.5 mol CO₂)/(mol Ala) was obtained at about (˜) 700 min, after which there was not much change in CO₂ absorption (FIG. 7A). Ala carbamate was also found to form first in the Ala-NaOH—H₂O solution, and the amount of Ala carbamate increased almost linearly with increasing CO₂ absorption time until 180 min, after which the amount of Ala carbamate decreased almost linearly with increasing CO₂ absorption time during 180-480 min (FIG. 7B). Meanwhile, no bicarbonate was detected until 180 min after which the amount of bicarbonate increased almost linearly with increasing CO₂ absorption time (FIG. 7B).

In the CSTR studies, the CO₂ absorption capacities of both MEA-H₂O and NaOH—H₂O control increased linearly with increasing CO₂ absorption time until 400 min, at which time their capacities were ˜(0.50 mol CO₂)/(mol MEA) and (0.43 mol CO₂)/(mol NaOH), respectively (FIG. 7A). After 400 min, there was almost no change in the CO₂ absorption capacity in MEA-H₂O solution and a very small but noticeable increase in NaOH—H₂O solution (FIG. 7A). Compared to both MEA-H₂O and NaOH—H₂O solutions, Ala-NaOH—H₂O solution had much faster absorption kinetics in its first absorption stage (I) (FIG. 7A).

TABLE 1 Species in Ala—NaOH—H₂O, MEA—H₂O and NaOH—H₂O control solutions after absorbing CO₂ for 700 min. Carbamate Bicarbonate Carbonate (mol/ (mol/ (mol/ Solvents mol) (%*) mol) (%*) mol) (%*) MEA (30 wt %) 0.35 94.6 0.02  5.4 0 0 Ala—NaOH—H₂O 0.21 12.1 1.52 87.9 0 0 NaOH control 0 0 0.11 20.8 0.42 79.2 *Percentage among the species of carbamate, bicarbonate, and carbonate.

In addition, after reacting with CO₂, the MEA-H₂O solution had a dominant MEA carbamate (94.6 wt % [weight percent]) with a very small portion of bicarbonate (5.4 wt %), the NaOH—H₂O solution had mainly carbonate (79.2 wt %) together with a significant amount of bicarbonate (20.8 wt %), and the Ala-NaOH—H₂O solution had dominant bicarbonate (87.9 wt %) with a small portion of Ala carbamate (12.1 wt %) and no carbonate at all (Table 1).

Taken together, our studies showed that Ala played three key roles in CO₂ absorption in the Ala-NaOH—H₂O system including (i) reacting with CO₂ to form Ala carbamate and bicarbonate resulting in high CO₂ absolution capacity, (ii) resulting in the formation of unique nanomaterials, and (iii) inhibiting the formation of carbonate from CO2 reacting with NaOH, based on the following evidence: (a) Ala carbamate formed first in the absorption process which subsequently hydrolyzed into bicarbonate, (b) no carbonate was ever observed in Ala-NaOH—H₂O solutions while the NaOH—H₂O control (without Ala) solution had carbonate dominance upon CO₂ absorption, and (c) under the same conditions, mainly large crystals of NaHCO₃ (FIG. 8) were observed in the NaOH—H₂O control solutions. NaOH was also found to play an important role in the Ala-NaOH—H₂O system by deprotonating protonated amino acids to enable Ala to react and absorb CO₂ based on the following evidence: Without NaOH, only negligible CO₂ absorption was detected in the AlaH₂O solution (FIG. 9) while very high capacities [e.g. (1.55 mol CO₂)/(mol Ala) in the simulated flue gas] were obtained in Ala-NaOH—H₂O solution.

Comparison to the-State-of-the-Art Technologies.

MEA and NaOH have been extensively studied for removing CO₂. For instance, Skyonic (San Antonio, Tex.) has recently developed a electrochemical production process to create NaOH to capture CO₂,^([22,23]) aiming to capture CO₂ in the region of 75,000 tons per year. Compared to NaOH scrubbing, the present method of this invention employing this inventions SCAA solvent produces unique NaHCO₃ nanomaterials and showed much higher CO₂ capacity with less material consumption (Table 2).^([35]) Compared to MEA, the SCAA solvent of the present invention undergoes a unique self-concentrating process and produces NaHCO₃ nanomaterials and has similar CO₂ capacity (based on weight) and material consumption. The regeneration of bicarbonate is energy-saving compared to the regeneration of carbamate. In addition, compared to MEA, amino acids have much lower volatility (due to their ionic nature), higher surface tension, and lower toxicity.

TABLE 2 Material consumption and species in solid part: Comparison among Ala, NaOH, and MEA solutions. CO₂ loading Materials Solvents NaHCO₃ in solid consumption³ AANaOH 13.94 g 0.13 AA: Fully recycle; (30 wt %) (g CO₂/g Solution) NaOH: 0.17 (g/g solution)¹ NaOH  2.34 g 0.02 NaOH: 0.21 (20 wt %) (g CO₂/g solution) (g/g solution) MEA² — 0.11 MEA² (30 wt %) (g CO₂/g solution) (0.15 g/g solution) (No solid) ¹AA fully recycle was based or the reaction and rising procedure; NaOH consumption in 1 cycle was calculated based on reaction ²MEA: CO₂ loading is less than alanine system [0.11 (g CO₂/g solution)] ³NaOH is much cheaper than MEA

A Process to Capture CO₂ while Producing Amino Acid Nanofibers.

The aforementioned is about the production of unique NaHCO₃ nanofibers and nanoflowers. Besides NaHCO₃ nanomaterials, we also developed a process to fabricate amino acid nanofibers during CO₂ absorption. By tuning the Phe-NaOH—H₂O system, we produced large quantities of Phe nanofibers (FIG. 10) and achieved a significant CO₂ capture capacity (FIG. 11). NMR tests (FIG. 12) confirmed that the nanofibers were Phe (not NaHCO₃) and CO₂ was absorbed as NaHCO₃.

Those persons skilled in the art will understand that the present invention provides methods for innovative CO₂ capture and utilization including (i) turning CO₂ into NaHCO₃ nanofibers and nanoflowers, and provides (ii) self-concentrating NaHCO₃ nanomaterials for easy separation and reuse, and discloses (iii) methods that lead to both CO₂ absorption and amino acid nanofiber formation.

EXAMPLES OF USES OF THE DISCLOSED INVENTION

Market for Bicarhonate Nanomaterials:

(i) As new nanomaterials, sharing the nanomaterials market (>$11 billion a year with an impact of over $340 billion):

(ii) As temporary supports for drug encapsulation, which has a yearly market of billions of dollars. According to a recent report from Transparency Market Research, the micro- and nano-encapsulation market has a worldwide market of $4.77 billion in 2013 and was projected to increase to $9.13 billion in 2020. North America and Europe together held 70% of the global encapsulation market. More than 65% of the micro- and nano-encapsulation market in 2013 was for pharmaceuticals in which the encapsulation allows for targeted drug delivery and release, sustained and controlled release of active ingredients, and masking of chemicals odors. (iii) As a therapeutic drug, with improved efficacy due to its nano-size, to treat a variety of medical issues including, for example but not limited to, heartburn, indigestion, high acid levels in blood or urine, relief of insect-bite symptoms etc. It has a significant market:

Prevalence and Disease/Symptom Occurrence Medical and Other Costs Gastroesophageal ~7 million people ~3.1 million people reflux disease in the U.S. have some were hospitalized in (GERD), heart symptoms of GERD. the U.S. in 2004 for bum, or acid 60% of the adult GERD-related reflux population will symptoms, experience complications, some type of GERD and treatment. within a 12 month There are ~64.6 period and 2030% million prescriptions will have written for weekly symptoms. GERD medications in the U.S. on an annual basis. It's estimated by the American College of Gastroenterology that the symptoms of GERD result in almost $2 billion in lost productivity each week of the year. Dyspepsia Prevalance Rate: 98% of hospital (indigestion) ~3.5% or 9.5 million consultant episodes people in U.S. for dyspepsia Incidence: 6 million required hospital cases annually in admission in England U.S. 2002-03; data of U.S. not found. (iv) As nano-baking soda, having a market of 42 million tons in 2005. (v) To be used at the incinerator for flue gasses cleaning purposes (removal of acid components), thus avoiding the current expensive purchase of sodium bicarbonate. In addition, due to the easy removal (e.g. via heating at 50 degrees C. (Centigrade) or mild acid washing), bicarbonate nanomaterials may be used as templates to make unique hollow micro-nano-structured materials that can play an important role in cutting edge innovations for energy conversion and storage technologies such as for example but not limited to solar cells, fuel cells, lithium ion batteries and super capacitors [Energy Environ. Sci., 2012, 5, 5604-/8]. Market for Amino Acid Nanofibers: (i) Tissue engineering: amino acid nanofibers can be used as scaffolds for musculoskeletal tissue engineering (including bone, cartilage, ligament, and skeletal muscle), skin tissue engineering, vascular tissue engineering, neural tissue engineering, and as carriers for the controlled delivery of drugs, proteins, and DNA. The U.S. market for tissue engineering products for musculoskeletal applications (as an example) is $18 billion in 2010, and the total potential market for these products is expected to exceed $39 billion in the year 2019. (ii) Biomaterials such as wound dressing, hydrogels etc. The global wound care market is expected to reach $18.3 billion by 2019 from $15.6 billion in 2014. (iii) Filtration and catalyst supports, etc. As an example, application of filtration technologies in pharmaceutical and biotechnological as well as food and beverage laboratories has a market of $1,805 million in 2014 and is expected to grow at 7% from 2014 to 2019.

This invention will lead to the following uses:

This invention sets forth CO₂ capture technologies that not only will effectively and efficiently capture CO₂ but also will simultaneously convert CO₂ emission into unique nanomaterials and commercially valuable chemicals or produce amino acid nanofibers. Uses may include for example but not limited to:

-   -   Capture CO₂ from power plants, air, etc.;     -   Capture and convert CO₂ into commercial products including         nanomaterials. No catalysts are required for the CO₂ conversion;     -   Fabricate large quantities of unique nanomaterials including         organic and inorganic nanofibers, nanowires, and nanoparticles;     -   Produce baking soda or amino acid nanomaterials in large         quantities;     -   Capture CO₂ from air and enclosed environment such as space         station or space ship, submarine etc.;     -   Capture other greenhouse gases; and     -   Purify water etc. based on, for example, self-concentrating and         formation of precipitates.

The technology will be of great interest to power plants and natural gas companies and other resources that generate greenhouse gases (for CO₂ capture and utilization), and to companies that are interested in or selling new products and producing large quantities of NaHCO₃ nanomaterials and amino acid nanofibers.

Products would include for example but not limited to: Technology to convert CO₂, into products without the use of catalysts, technology to produce amino acid nanofibers during CO₂ absorption, commercial products for daily life or research uses such as baking soda, amino acid nanofibers, and NaHCO₃ nanomaterials.

REFERENCES

-   [1] Yang S, Lin X, Lewis W, Suyetin M, Bichoutskaia E, Parker J E,     et al. A partially interpenetrated metal-organic framework for     selective hysteretic sorption of carbon dioxide. Nature materials.     2012; 11:710-6. -   [2] Yue M, Hoshino Y, Ohshiro Y, Imamura K, Miura Y.     Temperature-Responsive Microgel Films as Reversible Carbon Dioxide     Absorbents in Wet Environment. Angew Chem-Ger Edit. 2014;     126:2692-5. -   [3] Pacala S, Socolow R. Stabilization wedges: Solving the climate     problem for the next 50 years with current technologies. Science.     2004; 305:968-72, -   [4] Lin L C, Berger A H, Martin R L, Kim J, Swisher J A, Jariwala K,     et al. In silico screening of carbon-capture materials. Nat Mater.     2012; 11:633-41. -   [5] Mauna Loa Observatory. Hawaii http://co2now.orti/ (2014). -   [6] Tollefson J. Growing agricultural benefits for climate. Nature.     2009; 462:966-. -   [7] 2030 framework for climate and energy policies.     http://eceuropaeu/clima/policies/2n3Q/index enhtm. 2014. -   [8] Chu S. Carbon Capture and Sequestration. Science. 2009;     325:1599. -   [9] Gao W-Y, Chen Y, Niu Y, Williams K, Cash L, Perez P J, et al.     Crystal Engineering of an nbo Topology Metal-Organic Framework for     Chemical Fixation of CO2 under Ambient Conditions. Angewandte Chemie     International Edition. 2014; 53:2615-9. -   [10] Mathieu P. The IPCC special report on carbon dioxide capture     and storage. ECOS 2006: Proceedings of the 19th International     Conference on Efficiency, Cost, Optimization, Simulation and     Environmental Impact of Energy Systems, Vols 1-3. 2006:1611-7. -   [11] Massood R Timothy, J. S., Nsakala ya, N. & Liljedahl, G. N.     Carbon Dioxide Capture from Existing Coal-Fired Power Plants     (National Energy Technology Laboratory, US Department of Energy,     2007). -   [12] D'Alessandro D M, Smit B, Long J R. Carbon Dioxide Capture:     Prospects for New Materials. Angew Chem int Edit. 2010; 49:6058-82. -   [13] Yong Z, Mata V G, Rodrigues A E. Adsorption of carbon dioxide     on chemically modified high surface area carbon-based adsorbents at     high temperature. Adsorption. 2001; 7:41-50. -   [14] Li B Y, Duan Y H, Luebke D, Morreale B. Advances in CO2 capture     technology: A patent review. Appl Energ. 2013; 102:1439-47. -   [15] MacDowell N, Florin N, Buchard A, Hallett J, Galindo A, Jackson     G, et al. An overview of CO2 capture technologies. Energy &     Environmental Science. 2010; 3:1645. -   [16] Anderson S, Newell R. Prospects for carbon capture and storage     technologies. Annu Rev Env Resour. 2004; 29:109-42. -   [17] Haszeldine R S. Carbon Capture and Storage: How Green Can Black     Be? Science, 2009; 325:1647-52. -   [18] Little M G, Jackson R B. Potential Impacts of Leakage from Deep     CO2 Geosequestration on Overlying Freshwater Aquifers. Environ Sci     Technol. 2010; 44:9225-32. -   [19] Kim S H, Kim K R Hong S H, Carbon Dioxide Capture and Use:     Organic Synthesis Using Carbon Dioxide from Exhaust Gas. Angew Chem     Int Edit. 2014; 53:771-4. -   [20] Moret S, Dyson P J, Laurenczy G. Direct synthesis of formic     acid from carbon dioxide by hydrogenation in acidic media. Nat     Commun. 2014; 5. -   [21] Behrens M, Studt F, Kasatkin I, Kuhl S, Havecker M,     Abild-Pedersen F, et al. The Active Site of Methanol Synthesis over     Cu/ZnO/Al2O3 Industrial Catalysts. Science. 2012; 336:893-7. -   [22] Damiani D, Litynski J T, Mcllvried H G, Vikara D M, Srivastava     R D. The US department of Energy's R&D program to reduce greenhouse     gas emissions through beneficial uses of carbon dioxide. Greenhouse     Gases: Science and Technology. 2012; 2:9-16. -   [23] Jones J D. Removing carbon dioxide from waste streams through     co-generation of carbonate and/or bicarbonate minerals. U.S. Pat.     No. 7,727,374; 2010. -   [24] Gebreeyessus G D, Kaba T, Chandravanshi B S. Removing carbon     dioxide from a stationary source through co-generation of     carbonate/bicarbonate: The case of Mugher cement factory. African     Journal of Environmental Science and Technology. 2014; 8:75-85. -   [25] Stauffer P H, Keating G N, Middleton R S, Viswanathan H S,     Berchtod K A, Singh R P, et al. Greening Coal: Breakthroughs and     Challenges in Carbon Capture and Storage. Environmental science &     technology. 2011; 45:8597-604. -   [26] Jiang B, Wang X, Gray M L, Duan Y, Luebke D, Li B. Development     of amino acid and amino acid-complex based solid sorbents for CO2     capture. Applied Energy. 2013; 109:112-8. -   [27] Wang X, Akhmedov N G, Duan Y, Luebke D, Li B. Immobilization of     amino acid ionic liquids into nanoporous microspheres as robust     sorbents for CO2 capture. Journal of Materials Chemistry A. 2013;     1:2978-82. -   [28] Wang X, Akhmedov N G, Duan Y, Luebke D, Hopkinson D, Li B.     Amino acid-fimctionalized ionic liquid solid sorbents for     post-combustion carbon capture. ACS applied materials & interfaces.     2013; 5:8670-7. -   [29] Mufioz D M, Portugal A F, Lozano A E, Jose G, de Abajo J. New     liquid absorbents for the removal of CO2 from gas mixtures. Energy     Environ Sci. 2009; 2:883-91. -   [30] Jiang B B, DeFuseo E, Li B Y. Polypeptide Multilayer Film     Co-Delivers Oppositely-Charged Drug Molecules in Sustained Manners.     Biomacromolecules. 2010; 11:3630-7. -   [31] Li B Y, Jiang B B, Boyce B M, Lindsey B A. Multilayer     polypeptide nanoscale coatings incorporating IL-12 for the     prevention of biomedical device-associated infections. Biomaterials,     2009; 30:2552-8. -   [32] Jiang B B, Li B Y. Tunable drug loading and release from     polypeptide multilayer nanofilms. International journal of     nanomedicine. 2009; 4:37-53. -   [33] Jiang B B, Li B Y. Polypeptide Nanocoatings for Preventing     Dental and Orthopaedic Device-Associated Infection: pH-Induced     Antibiotic Capture, Release, and Antibiotic Efficacy. J Biomed.     Mater Res B. 2009; 88B:332-8. -   [34] Jiang B, Barnett J B, Li B. Advances in polyelectrolyte     multilayer nanofillms as tunable drug delivery systems.     Nanotechnology, science and applications. 2009; 2:21. -   [35] Knuutila H, Aronu U E, Kvamsdal H M, Chikukwa. A. Post     combustion CO2 capture with an amino acid salt. Energy Procedia.     2011; 4:1550-7. -   [36] Portugal A F, Sousa J M, Magalhaes F D, Mendes A. Solubility of     carbon dioxide in aqueous solutions of amino acid salts. Chemical     Engineering Science. 2009; 64:1993-2002. -   [37] Majchrowicz M E, Brilman D W F, Groeneveld M J, Precipitation     regime for selected amino acid salts for CO2 capture from flue     gases. Energy Procedia. 2009; 1:979-84. -   [38] Song H-J, Park S, Kim H, Gaur A, Park J-W, Lee S-J. Carbon     dioxide absorption characteristics of aqueous amino acid salt     solutions. International Journal of Greenhouse Gas Control. 2012;     11:64-72. -   [39] Kumar P S, Hogendoom J A, Feron P H M, Versteeg G F.     Equilibrium solubility of CO2 in aqueous potassium taurate     solutions: Part 1. Crystallization in carbon dioxide loaded aqueous     salt solutions of amino acids. Industrial & engineering chemistry     research. 2003; 42:2832-40. -   [40] Sanchez-Fernandez E, Mercader FdM, Misiak K, van der Ham L,     Linders M, Goetheer E. New Process Concepts for CO2 Capture based on     Precipitating Amino Acids. Energy Procedia. 2013; 37:1160-71. -   [41] Hook R J. An investigation of some sterically hindered amines     as potential carbon dioxide scrubbing compounds. Industrial &     engineering chemistry research. 1997; 36:1779-90. -   [42] Kumar P S, Hogendoom J A, Timmer S J, Feron P H M, Versteeg     G F. Equilibrium solubility of CO2 in aqueous potassium taurate     solutions: Part 2. Experimental V L E data and model. Industrial &     engineering chemistry research. 2003; 42:2841-52. -   [43] Tseng H C, Lee C Y, Weng W L, Shiah I M. Solubilities of amino     acids in water at various pH values under 298.15 K. Fluid Phase     Equilibria. 2009; 285:90-5. -   [44] Dunn M S, Ross F J, Read L S. The solubility of the amino acids     in water. Journal of Biological Chemistry. 1933; 103:579-95. -   [45] Needham T E, Paruta A, Gerraughty R. Solubility of amino acids     in pure solvent systems. J Pharm Sci. 1971; 60:565-7. -   [46] Bhaduri G A, Sitter L. Nickel nanoparticles catalyse reversible     hydration of carbon dioxide for mineralization carbon capture and     storage. Catal Sci Technol. 2013; 3:1234-9.

Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those persons skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims. 

What is claimed is:
 1. A method for converting carbon dioxide into NaHCO₃ nanofibers or nanoflowers consisting of subjecting a source of carbon dioxide to an amino acid containing aqueous salt solution consisting of an amino acid that is alanine, a base solvent that is either NaOH or KOH, and water without the use of a catalyst for producing a CO₂ lean phase of an alanine-NaOH or KOH solution and a CO₂ rich phase that is a NaHCO₃ nanomaterial precipitate.
 2. The method of claim 1 including wherein said amino acid containing aqueous salt solution is Ala-NaOH—H₂O.
 3. The method of claim 1 wherein said CO₂ rich phase is a NaHCO₃ solid product.
 4. The method of claim 3 wherein said NaHCO₃ solid product is subject to a purification process to form a purified bicarbonate solid product.
 5. The method of claim 4 including wherein said purified bicarbonate solid product is subjected to heat for achieving an increased concentration of a carbon dioxide gas. 